CN109336583B - Solid electrolyte for phosphorus determination probe and preparation method thereof - Google Patents

Solid electrolyte for phosphorus determination probe and preparation method thereof Download PDF

Info

Publication number
CN109336583B
CN109336583B CN201811252580.8A CN201811252580A CN109336583B CN 109336583 B CN109336583 B CN 109336583B CN 201811252580 A CN201811252580 A CN 201811252580A CN 109336583 B CN109336583 B CN 109336583B
Authority
CN
China
Prior art keywords
solid electrolyte
phosphorus
cao
determination probe
phosphorus determination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811252580.8A
Other languages
Chinese (zh)
Other versions
CN109336583A (en
Inventor
康雪
侯剑峰
滕飞
孙桂芳
王常珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University Qinhuangdao Branch
Original Assignee
Northeastern University Qinhuangdao Branch
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University Qinhuangdao Branch filed Critical Northeastern University Qinhuangdao Branch
Priority to CN201811252580.8A priority Critical patent/CN109336583B/en
Publication of CN109336583A publication Critical patent/CN109336583A/en
Application granted granted Critical
Publication of CN109336583B publication Critical patent/CN109336583B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on calcium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The inventionDiscloses a solid electrolyte for a phosphorus determination probe and a preparation method thereof, belonging to the technical field of phosphorus determination probe preparation. The invention provides a solid electrolyte for a phosphorus determination probe in a metal melt, aiming at solving the problems that an auxiliary electrode in the existing sensor is easy to fall off and the like, and the solid electrolyte is composed of CaO +4CaO & P2O5A material composition wherein the CaO content is less than 60%. The solid electrolyte material prepared by the invention has better thermal shock resistance and ideal conductivity, and can be applied to the detection of phosphorus in various metal melts, particularly copper and iron metal melts.

Description

Solid electrolyte for phosphorus determination probe and preparation method thereof
Technical Field
The invention relates to the technical field of solid electrolyte electrochemical sensors, in particular to a solid electrolyte for a phosphorus determination probe.
Background
Phosphorus is one of elements removed in metal smelting, and is easy to generate segregation, and cold brittleness is generated to influence the quality of metal. In the later stage of smelting, rephosphorization can be generated, the influence on the end point control of the metal smelting process is great, and the rapid test of the phosphorus content is the basis of the key smelting control and is also particularly important. The detection method in the current smelting process is divided into a chemical method and a spectral method, wherein the chemical method needs sampling, weighing, dissolving and titrating, so that the time is long, and the field production guidance is restricted; the use of spectroscopy is relatively time-saving and can be done in a few minutes, but accuracy is yet to be improved.
At present, no chemical sensor for detecting phosphorus determination probes in metal melts is reported to be used in production, in experimental research, ZrO (MgO) is mostly adopted as a solid electrolyte material, and an auxiliary electrode is coated outside to realize phosphorus determination operation, wherein the auxiliary electrolyte material comprises: al (Al)2O3+AlPO4Or CaO +4 CaO. P2O5Rare earth phosphates and Ca3(PO4)2And the like. CN103196974A A method for manufacturing a sensor for determining phosphorus, discloses a method for manufacturing a sensor for determining phosphorus in ZrO2(CaO) a phosphorus ion conductive solid electrolyte material is coated or thermally sprayed on two sides of the solid electrolyte, wherein the phosphorus ion conductive solid electrolyte comprises the following components in percentage by mass: CaO is 0-40%, 4 CaO. P2O5Is 100-60%. In the actual use process, because the auxiliary electrode material is easy to fall off,its field application is limited.
Fisher (FISCHER W A, JANKE D. Metallurgische Electrochemie, Stahleisen, Dusseldorf [ M ]. Berlin: Springer-Verlag, 1975: 321-2O5The solid electrolyte material is used for a phosphorus sensor to measure phosphorus in a metal melt, but the related stability and thermal shock resistance influence of the solid electrolyte material are not suitable for a phosphorus determination probe solid electrolyte.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the solid electrolyte of the phosphorus determination probe, which has enough mechanical property, stability and thermal shock resistance, has proper conductivity and can be used for detecting phosphorus in metal melts, particularly copper and iron melts; the invention also aims to provide the preparation method of the solid electrolyte for the phosphorus determination probe, which adopts a specific process flow to prepare the solid electrolyte for the phosphorus determination probe.
The invention is realized by the following technical scheme: a solid electrolyte for phosphorus-determining probe is prepared from CaO and 4CaO ∙ P2O5The material composition comprises CaO content less than 60%, and chemical composition xCaO + (1-x) 4CaO ∙ P2O5，x＜60%。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) CaCO is taken according to the molar ratio of 1-5.9:13(CaO) and CaHPO4∙2H2And (3) mechanically and uniformly mixing the O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 10-50 microns.
(2) And (2) heating the mixed powder in the step (1) to 1350 ℃ and 1550 ℃ at the heating rate of 3-10 ℃/min, sintering for 1-5h, and then cooling to room temperature in the dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
The invention has the beneficial effects.
(1) The solid electrolyte for the phosphorus determination probe is prepared by one-time sintering, and the material has better thermal shock resistance and ideal conductivity by controlling the mixing proportion of the raw materials. Compared with the prior art, the solid electrolyte for the phosphorus determination probe prepared by the invention does not need to be coated with a working layer, does not fall off in practical application, and is more suitable for application in industrial production; after the content of CaO is reduced to a proper range, the prepared solid electrolyte has better stability and thermal shock resistance and ideal conductivity.
(2) According to the preparation method of the solid electrolyte for the phosphorus determination probe, mechanical mixing is adopted for mixing, the particle medium diameter particle size of the obtained mixed powder is 10-50 microns, the particle size is moderate, the components are guaranteed to be uniform, the full reaction is easy, the particle size is easy to control, and the increase of the operation cost is avoided; in the sintering process, the solid electrolyte is heated to 1450-1580 ℃ at the heating rate of 3-8 ℃/min for sintering for 2-5 h, so that the sintering energy consumption is reduced, a pure monoclinic system structure can be obtained, and the obtained solid electrolyte is ensured to meet the use requirement of a phosphorus determination probe. The preparation method disclosed by the invention is simple in steps, easy to operate and implement, easy in control of reaction conditions, capable of reducing sintering energy consumption and capable of ensuring stable performance of the solid electrolyte.
Detailed Description
Example 1.
A solid electrolyte for phosphorus determination probe contains 25% CaO + 75% 4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Taking corresponding CaCO according to the molar ratio of 2.09:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 24 microns.
(2) And (2) heating the mixed powder in the step (1) to 1350 ℃ at a heating rate of 4 ℃/min, then sintering for 1h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
Example 2.
A solid electrolyte for phosphorus-fixing probe contains 35% of chemical componentsCaO + 65% 4CaO∙P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Weighing corresponding CaCO according to molar ratio of 2.76:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 28 microns.
(2) And (2) heating the mixed powder in the step (1) to 1400 ℃ at a heating rate of 5 ℃/min, then sintering for 5h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
Example 3.
A solid electrolyte for phosphorus determination probe contains 40% CaO + 60% 4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Taking corresponding CaCO according to a molar ratio of 3.18:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 34 microns.
(2) And (2) heating the mixed powder in the step (1) to 1450 ℃ at a heating rate of 3 ℃/min, then sintering for 3h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
Example 4.
A solid electrolyte for phosphorus determination probe contains 45% CaO + 55% 4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Weighing corresponding CaCO according to the molar ratio of 3.67:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 45 microns.
(2) And (2) heating the mixed powder in the step (1) to 1500 ℃ at a heating rate of 10 ℃/min, then sintering for 4h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
Example 5.
A solid electrolyte for phosphorus determination probe contains 50% CaO + 50% 4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Weighing corresponding CaCO according to molar ratio of 4.27:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 48 microns.
(2) And (2) heating the mixed powder in the step (1) to 1550 ℃ at a heating rate of 7 ℃/min, then sintering for 2h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus determination probe.
Example 6.
A solid electrolyte for phosphorus determination probe contains 55% CaO + 45% 4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Taking corresponding CaO and CaHPO according to the molar ratio of 5:14∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 41 microns.
(2) And (2) heating the mixed powder in the step (1) to 1550 ℃ at a heating rate of 6 ℃/min, then sintering for 3.5h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for the phosphorus-determining probe.
And (4) carrying out comparative experiments.
Comparative example 1.
A solid electrolyte for phosphorus determination comprises 65% CaO + 35%4CaO ∙ P2O5。
A preparation method of a solid electrolyte for a phosphorus determination probe comprises the following specific steps.
(1) Weighing corresponding CaCO according to the molar ratio of 7.07:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 28 microns.
(2) And (2) sintering the mixed powder in the step (1) at 1450 ℃ for 3h, and then cooling to room temperature in a dry air atmosphere to obtain the solid electrolyte for determining phosphorus.
Comparative example 2.
A phosphorus sensor comprises ZrO for measuring oxygen content in molten steel2(CaO) solid electrolyte in ZrO2(CaO) coating or thermal spraying a phosphorus ion conductive solid electrolyte material on both sides of the solid electrolyte; phosphorus ion conductive solid electrolyte comprises 40% of CaO and 60% of 4CaO ∙ P in percentage by mass2O5。
The preparation method of the phosphorus ion conductive solid electrolyte comprises the following specific steps.
(1) CaCO is taken according to a molar ratio of 3.18:13And CaHPO4∙2H2And (3) mechanically and uniformly mixing O powder, wherein the particle medium diameter granularity of the obtained mixed powder is 30 microns.
(2) And (2) sintering the mixed powder in the step (1) at 1450 ℃ for 3h, and then cooling to room temperature in a dry air atmosphere to obtain the phosphorus ion conductive solid electrolyte.
The phosphorus sensor prepared in comparative example 2 was used for on-line detection of phosphorus content in molten steel, and it was found in the experiment that slight peeling of the coated solid electrolyte occurred.
The solid electrolytes prepared in examples and comparative examples were tested separately, and the test results are shown in the following table.
Figure 534324DEST_PATH_IMAGE001

Claims (1)

1. The solid electrolyte for the phosphorus determination probe is characterized by comprising CaO +4 CaO.P2O5The material comprises 25-60% of CaO by mass, and the chemical composition is xCaO + (1-x) 4 CaO.P2O5，25%＜x＜ 60%；
The solid electrolyte comprises the following specific preparation steps:
(1) CaCO is taken according to the molar ratio of 1-5.9:13Or CaO and CaHPO4·2H2The O powder is mechanically and uniformly mixed, and the particle medium diameter granularity of the obtained mixed powder is 10-50 microns;
(2) and (2) heating the mixed powder in the step (1) to the temperature of 1350-.
CN201811252580.8A 2018-10-25 2018-10-25 Solid electrolyte for phosphorus determination probe and preparation method thereof Active CN109336583B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811252580.8A CN109336583B (en) 2018-10-25 2018-10-25 Solid electrolyte for phosphorus determination probe and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811252580.8A CN109336583B (en) 2018-10-25 2018-10-25 Solid electrolyte for phosphorus determination probe and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109336583A CN109336583A (en) 2019-02-15
CN109336583B true CN109336583B (en) 2021-09-07

Family

ID=65312374

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811252580.8A Active CN109336583B (en) 2018-10-25 2018-10-25 Solid electrolyte for phosphorus determination probe and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109336583B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62224621A (en) * 1986-03-26 1987-10-02 Sumitomo Metal Ind Ltd Dephosphorization method for molten pig iron
CN103196974A (en) * 2012-01-10 2013-07-10 东北大学 Manufacturing method of sensor for phosphorus determination

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62224621A (en) * 1986-03-26 1987-10-02 Sumitomo Metal Ind Ltd Dephosphorization method for molten pig iron
CN103196974A (en) * 2012-01-10 2013-07-10 东北大学 Manufacturing method of sensor for phosphorus determination

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"碳饱和铁液中磷的传感法研究";康雪 等;《中国稀土学报》;20080831;第26卷;第381-382页 *

Also Published As

Publication number Publication date
CN109336583A (en) 2019-02-15

Similar Documents

Publication Publication Date Title
Schwandt et al. Solid state electrochemical gas sensor for the quantitative determination of carbon dioxide
Yang et al. Influence of phosphorus sources on lithium ion conducting performance in the system of Li2O–Al2O3–GeO2–P2O5 glass–ceramics
CN101196488A (en) Sulfur determination probe for molten metal
Zhou et al. Synthesis, processing and characterization of calcia-stabilized zirconia solid electrolytes for oxygen sensing applications
CN109503197A (en) A kind of preparation method of calcium hexaluminate porous ceramics
CN109336583B (en) Solid electrolyte for phosphorus determination probe and preparation method thereof
Tian et al. Effect of sintering atmosphere on corrosion resistance of Ni/(NiFe2O4–10NiO) cermet inert anode for aluminum electrolysis
Gao et al. Study on electrolytic reduction with controlled oxygen flow for iron from molten oxide slag containing FeO
CN103207228A (en) Molten steel phosphorus sensor auxiliary electrode manufacturing method
Kruidhof et al. Thermochemical stability and nonstoichiometry of erbia-stabilized bismuth oxide
CN109053186B (en) Lanthanum-doped solid electrolyte for phosphorus determination probe and preparation method thereof
CN106007714B (en) Solid electrolyte for hydrogen determination probe in aluminum and aluminum alloy melt and preparation method thereof
CN106187151A (en) A kind of aluminum doped yttrium zinc oxide ceramic target and preparation method thereof
CN108918615A (en) A kind of electrochemical sensor and preparation method thereof measuring manganese in molten steel/iron liquid
CN109060775A (en) A kind of steel-making measuring method of Ti content in raw and auxiliary material
Wen et al. Electrical conductivity behavior of ZrO2-MgO-Y2O3 ceramic: Effect of heat treatment temperature
Chen et al. Effect of CaO additive on the interfacial reaction between the BaZrO 3 refractory and titanium enrichment melt
Tian et al. Effect of sintering atmosphere on corrosion resistance of NiFe2O4 ceramic in Na3AlF6–Al2O3 melt
Yao et al. Sodium activity determinations in molten 99.5% aluminium using solid electrolytes
CN101762631A (en) Aluminum sensor used in hot dip galvanizing process and preparation method thereof
CN112964830A (en) Determination of SiO in metallurgical slag2Activity coefficient and method of activity
Kawabata et al. Activities of phosphorous in liquid Ni+ P alloys saturated with solid nickel
Mauvy et al. Electrochemical study of the Nd1. 95NiO4+ δ/oxide electrolyte interface
Wen et al. Preparation and characterization of (Ca2+, Al3+)-infiltrated CaO-Al2O3 auxiliary electrode for electrochemical sulfur sensor
Kang et al. Solid State Electrochemical Phosphorus Sensor for Carbon-Saturated Iron Melts

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant